Susana Tostón Serrano ([email protected])
Department of Chemical Engineering – Faculty of Environmental Sciences and
Biochemistry. UCLM. Toledo (Spain)
INDEX
1. Introduction Approaching the problem Alternative proposal CO2 photocatalytic conversion
2. Experimental High pressure synthesis of photocatalysts Catalyst characterization Photocatalytic activity assessment Analysis of conversion products 3. Results Photocatalyst physicochemical properties (DRX, DR- UV-Vis) Compound production in CO2 reduction 4. Conclusions
Introduction
APPROACHING THE PROBLEM
IPCC, 5th Assessment Report , Working Group I, 2013 (Figure subject to final copy edit)
Reduce CO2 emission rate in order to
minimize impacts
Introduction
APPROACHING THE PROBLEM
International Energy Outlook 2013
Liquid fuels
Coal
Natural gas
projections history
Introduction
ALTERNATIVE PROPOSAL
CO2 PHOTOCATALYTIC CONVERSION
CO2
capture and recycling
REDUCCIREDUCCIÓÓN N DE GASES DE DE GASES DE
EFECTO EFECTO
INVERNADEROINVERNADERO
REDUCCIREDUCCIÓÓN DE LA N DE LA DEFORESTACIDEFORESTACIÓÓNN
CAPTURA Y CAPTURA Y
ALMACENAMIENTO COALMACENAMIENTO CO22
FUENTES FUENTES ALTERNATIVAS ALTERNATIVAS
DE ENERGDE ENERGÍÍAA
MEJORA MEJORA EFICIENCIA EFICIENCIA
ENERGENERGÉÉTICATICA
CAPTURA Y CAPTURA Y
CONVERSICONVERSIÓÓN CON CO22
REDUCCIREDUCCIÓÓN N DE GASES DE DE GASES DE
EFECTO EFECTO
INVERNADEROINVERNADERO
REDUCCIREDUCCIÓÓN DE LA N DE LA DEFORESTACIDEFORESTACIÓÓNN
CAPTURA Y CAPTURA Y
ALMACENAMIENTO COALMACENAMIENTO CO22
FUENTES FUENTES ALTERNATIVAS ALTERNATIVAS
DE ENERGDE ENERGÍÍAA
MEJORA MEJORA EFICIENCIA EFICIENCIA
ENERGENERGÉÉTICATICA
CAPTURA Y CAPTURA Y
CONVERSICONVERSIÓÓN CON CO22
Decreasing deforestation
REDUCCIREDUCCIÓÓN N DE GASES DE DE GASES DE
EFECTO EFECTO
INVERNADEROINVERNADERO
REDUCCIREDUCCIÓÓN DE LA N DE LA DEFORESTACIDEFORESTACIÓÓNN
CAPTURA Y CAPTURA Y
ALMACENAMIENTO COALMACENAMIENTO CO22
FUENTES FUENTES ALTERNATIVAS ALTERNATIVAS
DE ENERGDE ENERGÍÍAA
MEJORA MEJORA EFICIENCIA EFICIENCIA
ENERGENERGÉÉTICATICA
CAPTURA Y CAPTURA Y
CONVERSICONVERSIÓÓN CON CO22
REDUCCIREDUCCIÓÓN N DE GASES DE DE GASES DE
EFECTO EFECTO
INVERNADEROINVERNADERO
REDUCCIREDUCCIÓÓN DE LA N DE LA DEFORESTACIDEFORESTACIÓÓNN
CAPTURA Y CAPTURA Y
ALMACENAMIENTO COALMACENAMIENTO CO22
FUENTES FUENTES ALTERNATIVAS ALTERNATIVAS
DE ENERGDE ENERGÍÍAA
MEJORA MEJORA EFICIENCIA EFICIENCIA
ENERGENERGÉÉTICATICA
CAPTURA Y CAPTURA Y
CONVERSICONVERSIÓÓN CON CO22
Improved energy
efficiency
REDUCCIREDUCCIÓÓN N DE GASES DE DE GASES DE
EFECTO EFECTO
INVERNADEROINVERNADERO
REDUCCIREDUCCIÓÓN DE LA N DE LA DEFORESTACIDEFORESTACIÓÓNN
CAPTURA Y CAPTURA Y
ALMACENAMIENTO COALMACENAMIENTO CO22
FUENTES FUENTES ALTERNATIVAS ALTERNATIVAS
DE ENERGDE ENERGÍÍAA
MEJORA MEJORA EFICIENCIA EFICIENCIA
ENERGENERGÉÉTICATICA
CAPTURA Y CAPTURA Y
CONVERSICONVERSIÓÓN CON CO22
REDUCCIREDUCCIÓÓN N DE GASES DE DE GASES DE
EFECTO EFECTO
INVERNADEROINVERNADERO
REDUCCIREDUCCIÓÓN DE LA N DE LA DEFORESTACIDEFORESTACIÓÓNN
CAPTURA Y CAPTURA Y
ALMACENAMIENTO COALMACENAMIENTO CO22
FUENTES FUENTES ALTERNATIVAS ALTERNATIVAS
DE ENERGDE ENERGÍÍAA
MEJORA MEJORA EFICIENCIA EFICIENCIA
ENERGENERGÉÉTICATICA
CAPTURA Y CAPTURA Y
CONVERSICONVERSIÓÓN CON CO22
CO2
capture and storage (CCS)
REDUCCIREDUCCIÓÓN N DE GASES DE DE GASES DE
EFECTO EFECTO
INVERNADEROINVERNADERO
REDUCCIREDUCCIÓÓN DE LA N DE LA DEFORESTACIDEFORESTACIÓÓNN
CAPTURA Y CAPTURA Y
ALMACENAMIENTO COALMACENAMIENTO CO22
FUENTES FUENTES ALTERNATIVAS ALTERNATIVAS
DE ENERGDE ENERGÍÍAA
MEJORA MEJORA EFICIENCIA EFICIENCIA
ENERGENERGÉÉTICATICA
CAPTURA Y CAPTURA Y
CONVERSICONVERSIÓÓN CON CO22
REDUCCIREDUCCIÓÓN N DE GASES DE DE GASES DE
EFECTO EFECTO
INVERNADEROINVERNADERO
REDUCCIREDUCCIÓÓN DE LA N DE LA DEFORESTACIDEFORESTACIÓÓNN
CAPTURA Y CAPTURA Y
ALMACENAMIENTO COALMACENAMIENTO CO22
FUENTES FUENTES ALTERNATIVAS ALTERNATIVAS
DE ENERGDE ENERGÍÍAA
MEJORA MEJORA EFICIENCIA EFICIENCIA
ENERGENERGÉÉTICATICA
CAPTURA Y CAPTURA Y
CONVERSICONVERSIÓÓN CON CO22
REDUCCIREDUCCIÓÓN N DE GASES DE DE GASES DE
EFECTO EFECTO
INVERNADEROINVERNADERO
REDUCCIREDUCCIÓÓN DE LA N DE LA DEFORESTACIDEFORESTACIÓÓNN
CAPTURA Y CAPTURA Y
ALMACENAMIENTO COALMACENAMIENTO CO22
FUENTES FUENTES ALTERNATIVAS ALTERNATIVAS
DE ENERGDE ENERGÍÍAA
MEJORA MEJORA EFICIENCIA EFICIENCIA
ENERGENERGÉÉTICATICA
CAPTURA Y CAPTURA Y
CONVERSICONVERSIÓÓN CON CO22
REDUCCIREDUCCIÓÓN N DE GASES DE DE GASES DE
EFECTO EFECTO
INVERNADEROINVERNADERO
REDUCCIREDUCCIÓÓN DE LA N DE LA DEFORESTACIDEFORESTACIÓÓNN
CAPTURA Y CAPTURA Y
ALMACENAMIENTO COALMACENAMIENTO CO22
FUENTES FUENTES ALTERNATIVAS ALTERNATIVAS
DE ENERGDE ENERGÍÍAA
MEJORA MEJORA EFICIENCIA EFICIENCIA
ENERGENERGÉÉTICATICA
CAPTURA Y CAPTURA Y
CONVERSICONVERSIÓÓN CON CO22
Alternative energy sources
Reduction of greenhouse
gases
Introduction
CO2 RECYCLING CO2 PHOTOCATALYTIC CONVERSION
Conduction band
Valence band
h+
e-
Gap Band hv
Incre
asing E
CO2 + H2O
CH4 CH2O CH3COOH
TiO2 nanoparticle
hv
Doping metal
Photocatalyst TiO2
Ideal candidate photocatalysis
Experimental
HIGH PRESSURE SYNTHESIS OF PHOTOCATALYSTS
EXPERIMENTAL SETUP SYNTHESIS PROCESS
Ti{OCH(CH3)2}4 / DIPBAT
2-propanol/ Ethanol
Acetylacetonate Cu/Pd
Drying at 105 ° C
Calcination at 400 ° C, 6h
Thermohydrolysis 2 h
200 bar 300 °C
Cu/Pd/TiO2
Ad hoc design based on Alonso et al., 2009
Experimental
CATALYST CHARACTERIZATION
X RAY DIFFRACTION UV-Vis SPECTROSCOPY DIFFUSE REFLECTANCE
CRYSTALLINITY ABSORPTION THRESHOLD
CRYSTALLINE PHASES: ANATASE/RUTILE
BAND GAP ENERGY
Experimental
PHOTOCATALYTIC ACTIVITY ASSESSMENT
EXPERIMENTAL SETUP SOLAR REACTOR
Quartz window
Photocatalytic reactor
Adapted from Varghese y col., 2009
Ad hoc design based on Zhang et al., 2011
Dew point Gauge
Xe Arc Lamp
GC-TCD/FID
Stainless Steel Wall
Experimental
ANALYSIS OF CONVERSION PRODUCTS
Agilent MSD 5975C: - Unknown compounds
Agilent GC 7890A: - 2 TCD detectors - FID detector with
methanizer
- Gases: H2, O2, CO, CO2
- Low-molecular-weight HCs: C1 – C7
- LMW alcohols, esters and ketones
Results
PHOTOCATALYST CHARACTERIZATION (I)
X RAY DIFFRACTION
Lower peak height and resolution
0
200
400
600
800
1000
1200
1400
20 30 40 50 60 70 80
Ángulo (2 Theta)
Cu
en
tas
-600
-400
-200
0
200
400
600
800
TiO2 sintet. TTIP-ISOP. TiO2 Comercial
TTIP-Isopropanol
A
A A
A A A R
Commercial TiO2
A: Anatase phase R: Rutile phase
Co
un
ts
Angle (2 Theta)
0
200
400
600
800
1000
1200
1400
20 30 40 50 60 70 80
Ángulo (2 Theta)
Cu
en
tas
-600
-400
-200
0
200
400
600
800
TiO2 sintet. TTIP-Etanol TiO2 Comercial
TTIP-Ethanol
Commercial TiO2
0
200
400
600
800
1000
1200
1400
20 30 40 50 60 70 80
Ángulo (2 Theta)
Cu
en
tas
-600
-400
-200
0
200
400
600
800
TiO2 sintet. DIPBAT-ISOP. TiO2 Comercial
DIPBAT-Isop.
0
200
400
600
800
1000
1200
1400
20 30 40 50 60 70 80
Ángulo (2 Theta)
Cu
en
tas
-600
-400
-200
0
200
400
600
800
TiO2 sintet. DIPBAT-Etanol TiO2 Comercial
DIPBAT-Ethanol
Co
un
ts
Angle (2 Theta) C
ou
nts
Angle (2 Theta)
Angle (2 Theta)
Co
un
ts
Commercial TiO2
Commercial TiO2
Higher crystallinity
Results
Visible
PHOTOCATALYST CHARACTERIZATION (II)
UV-Vis SPECTROSCOPY DIFFUSE REFLECTANCE
0
0,5
1
1,5
2
2,5
3
200 250 300 350 400 450 500 550 600 650 700
Longitud de onda (nm)
Ab
so
rba
nc
ia (
u.a
.)
PRECURSOR:
DIPBAT
PRECURSOR:
TTIP
TiO2 comercialCommercial TiO2
Precursor TTIP
Precursor DIPBAT
Ab
sorb
ance
(a.
u.)
Wavelength (nm)
Results
Visible
PHOTOCATALYST CHARACTERIZATION (II)
UV-Vis SPECTROSCOPY DIFFUSE REFLECTANCE
Ab
sorb
ance
(a.
u.)
COMMERCIAL TiO2
Wavelength (nm)
Cu CONTENT
Results
Reaction products identified in preliminary tests
CONTROL SAMPLES
SAMPLE AFTER PHOTOCATALYTIC REACTION
tR: 6,79 min
Ethane
tR: 11,95 min
Methane
tR: 12,68 min
CO
tR: 14,09 min
Propylene
tR: 15,73 min
Propane
PHOTOCATALYTIC ACTIVITY ASSESSMENT
Conclusions
XRD → among undoped synthesis combinations, TTIP-isopropanol shows the highest crystallinity, very similar to commercial TiO2. All combinations, crystalline phase anatase → enhance photocatalytic process
Conclusions
XRD → among undoped synthesis combinations, TTIP-isopropanol shows the highest crystallinity, very similar to commercial TiO2. All combinations, crystalline phase anatase → enhance photocatalytic process
UV-Vis Spectroscopy DR → DIPBAT catalysts, higher absorbance at visible wavelenghts, without decreasing in UV region → more effective use of energy from Xe arc lamp (solar spectrum)
Conclusions
XRD → among undoped synthesis combinations, TTIP-isopropanol shows the highest crystallinity, very similar to commercial TiO2. All combinations, crystalline phase anatase → enhance photocatalytic process
UV-Vis Spectroscopy DR → DIPBAT catalysts, higher absorbance at visible wavelenghts without decreasing in UV region → more effective use of energy from Xe arc lamp (solar spectrum)
Cu-doped photocatalysts UV-Vis DR → progressive increase in absorbance in visible region up to 2% wt. of metal
Conclusions
XRD → among undoped synthesis combinations, TTIP-isopropanol shows the highest crystallinity, very similar to commercial TiO2. All combinations, crystalline phase anatase → enhance photocatalytic process
UV-Vis Spectroscopy DR → DIPBAT catalysts, higher absorbance at visible wavelenghts without decreasing in UV region → more effective use of energy from Xe arc lamp (solar spectrum)
Cu-doped photocatalysts UV-Vis DR → progressive increase in absorbance in visible region up to 2% wt. of metal
Preliminary PC tests → main reaction products → methane and CO; ethane, propylene and propane in lower concentrations
Conclusions
XRD → among undoped synthesis combinations, TTIP-isopropanol shows the highest crystallinity, very similar to commercial TiO2. All combinations, crystalline phase anatase → enhance photocatalytic process
UV-Vis Spectroscopy DR → DIPBAT catalysts, higher absorbance at visible wavelenghts without decreasing in UV region → more effective use of energy from Xe arc lamp (solar spectrum)
Cu-doped photocatalysts UV-Vis DR → progressive increase in absorbance in visible region up to 2% wt. of metal
Preliminary PC tests → main reaction products → methane and CO; ethane, propylene and propane in lower concentrations
Further experiments of CO2 reduction → selection of the best precursor-alcohol combination and optimum metal load. In addition, further tests with other metals (Pd)
Conclusions
XRD → among undoped synthesis combinations, TTIP-isopropanol shows the highest crystallinity, very similar to commercial TiO2. All combinations, crystalline phase anatase → enhance photocatalytic process
UV-Vis Spectroscopy DR → DIPBAT catalysts, higher absorbance at visible wavelenghts without decreasing in UV region → more effective use of energy from Xe arc lamp (solar spectrum)
Cu-doped photocatalysts UV-Vis DR → progressive increase in absorbance in visible region up to 2% wt. of metal
Preliminary PC tests → main reaction products → methane and CO; ethane, propylene and propane in lower concentrations
Further experiments of CO2 reduction → selection of the best precursor-alcohol combination and optimum metal load. In addition, further tests with other metals (Pd)
Future stage of the project, energy source → Solar radiation
Conclusions
XRD → among undoped synthesis combinations, TTIP-isopropanol shows the highest crystallinity, very similar to commercial TiO2. All combinations, crystalline phase anatase → enhance photocatalytic process
UV-Vis Spectroscopy DR → DIPBAT catalysts, higher absorbance at visible wavelenghts without decreasing in UV region → more effective use of energy from Xe arc lamp (solar spectrum)
Cu-doped photocatalysts UV-Vis DR → progressive increase in absorbance in visible region up to 2% wt. of metal
Preliminary PC tests → main reaction products → methane and CO; ethane, propylene and propane in lower concentrations
Further experiments of CO2 reduction → selection of the best precursor-alcohol combination and optimum metal load. In addition, further tests with other metals (Pd)
Future stage of the project, energy source → Solar radiation
This process can constitute an interesting alternative technology to CO2 storage: valorization of the gas, possibility to obtain fuels (recycling), environmentally friendly.
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